Influence of a magnetic field on deposition of diamond-like carbon films

Received: 17 February 1998/Accepted: 25 May 1998     

Effect of deposition voltage on the field emission properties of electrodeposited diamond-like carbon films

Diamond-like carbon (DLC) films were deposited on Al substrates by electrodeposition technique under various voltages. The surface morphology and compositions of synthesized films were characterized by scanning electron microscopy and Raman spectroscopy. With the increase of deposition voltage, the sp² phase concentration decreased and the surface morphology changed dramatically. The influence of deposition voltage on the field electron emission (FEE) properties of DLC films was not monotonic due to two adverse effects of deposition voltage on the surface morphology and compositions. The DLC film deposited under 1200 V exhibited optimum FEE property, including a lowest threshold field of 13 V/μm and a largest emission current density of 904.8 μA/cm² at 23.5 V/μm.     

Tribological properties of diamond-like carbon films deposited by pulsed laser arc deposition

A novel method, pulsed laser arc deposition combining the advantages of pulsed laser deposition and cathode vacuum arc techniques, was used to deposit the diamond-like carbon (DLC) nanofilms with different thicknesses. Spectroscopic ellipsometer, Auger electron spectroscopy, x-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy, scanning electron microscopy and multi-functional friction and wear tester were employed to investigate the physical and tribological properties of the deposited films. The results show that the deposited films are amorphous and the sp$^{2}$, sp$^{3}$ and C--O bonds at the top surface of the films are identified. The Raman peak intensity and surface roughness increase with increasing film thickness. Friction coefficients are about 0.1, 0.15, 0.18, when the film thicknesses are in the range of 17--21~nm, 30--57~nm, 67--123~nm, respectively. This is attributed to the united effects of substrate and surface roughness. The wear mechanism of DLC films is mainly abrasive wear when film thickness is in the range of 17--41~nm, while it transforms to abrasive and adhesive wear, when the film thickness lies between 72 and 123~nm.     

Short-pulse laser deposition of diamond-like carbon thin films

The high intensities present in and the non-thermal nature of ultrashort-pulse laser ablation provide a nearly ideal source for thin-film deposition. The high kinetic energies and high ion content in the ablation plume suggest that it would be useful for the creation of diamond thin films. We used a 120 fs, 3 W, 1 kHz laser to ablate a graphite target and characterized the resulting films. We were able to grow amorphous films of up to 18 7m thick and free from graphite particulates with no annealing necessary and at rates up to 25 7m/hr. The films had 40-50% sp³ bonds as measured by using EELS and had properties typical of PLD-generated diamond-like carbon films.     

Laser fluence dependence of the elastic properties of diamond-like carbon films prepared by pulsed-laser deposition

We studied the temperature dependence of internal friction of variety of amorphous diamond-like carbon films prepared by pulsed-laser deposition. Like the most of amorphous solids, the internal friction below 10 K exhibits a temperature independent plateau, which is caused by the atomic tunnelling states—a measure of structure disorder. In this work, we have varied the concentration of sp³ versus sp² carbon atoms by increasing laser fluence from 1.5 to 30 J/cm². Our results show that the internal friction has a nonmonotonic dependence on sp³/sp² ratio with the values of the internal friction plateaus varying between 6×10⁻⁵ and 1.1×10⁻⁴. We explain our findings as a result of a possible competition between the increase of atomic bonding and the increase of internal strain in the films, both of which are important in determining the tunneling states in amorphous solids. The importance of the internal strain in diamond-like carbon films is consistent with our previous study on laser fluence, doping, and annealing, which we will review as well. In contrast, no significant dependence of laser fluence is found in shear moduli of the films, which vary between 220 and 250 GPa.     

Chromium-doped diamond-like carbon films deposited by dual-pulsed laser deposition

Diamond-like carbon (DLC) and Cr-doped diamond-like carbon layers were studied. DLC and Cr-DLC were deposited on silicon and titanium substrates (Ti-6Al-4V) by dual-pulsed laser ablation using two KrF excimer lasers and two targets (graphite and chromium). The composition was analyzed using wavelength-dependent X-ray spectroscopy. The Cr content increased from 2.2 to 17.9 at%. The topology and surface properties as roughness of layers were studied using scanning electron microscopy and atomic force microscopy. With the chromium concentration increased the roughness and the number of droplets. Carbon and chromium bonds were determined by Raman spectroscopy. With an increase in chromium content the I _D/I _G ratio increased. Mechanical properties of DLC films with various chromium content were evaluated. Hardness (reduced Young’s modulus) was determined by nanoindentation and reached of 51 GPa (309 GPa). Films adhesion was studied using scratch test and with concentration of chromium increased up to 20 N.     

Influence of sulfidation treatment on the structure and tribological properties of nitrogen-doped diamond-like carbon films

The nitrogen-doped diamond-like carbon (DLC) films were deposited on high speed steel (HSS) substrates in the direct current unbalanced magnetron sputtering system. Sulphurized layer was formed on the surface of DLC films by means of liquid sulfidation in the intermixture of urea and thiourea solution in order to improve the tribological properties of DLC films. The influence of sulfidation treatment on the structure and tribological properties of DLC films was investigated in this work. The structure and wear surface morphology of DLC films were analyzed by Raman spectroscopy, XPS and SEM, respectively. It reveals that the treated films are smooth and uniform; and sulfur atoms are bonded chemically. The treated films have broader distribution of Raman spectra in the range of 1000-1800 cm⁻¹ and higher I_D/I_G ratio than the untreated films as a result of the appearance of the crystalline graphite structure after the sulfidation treatment. It is showed that the sp² relative content increase in the treated films from the XPS measurement. The Raman results are consistent with the XPS results. The tribological properties of DLC films were investigated using a ball-on-disk rotating friction and wear tester under dry friction conditions. It is found that the sulfidation concentration plays an important part in the tribological properties of the treated DLC films. The results showed the treated films with low sulfidation concentration have a lower friction coefficient (0.1) than the treated films with high sulfidation concentration (0.26) and the untreated films (0.27) under the same friction testing conditions, which can be attributed to both the presence of sulfur-containing materials and the forming of the mechanical alloyed layer on the wear surface. Adding the dry nitrogen to the sliding surface in the testing system helps the friction coefficient of the treated films with low sulfidation concentration to decrease to 0.04 further in this work. On the basis of the experimental results, it is indicated that the liquid sulfidation technique, which is low-cost, non-polluting and convenience, would be an appropriate method for the surface treatment of DLC films.     

电化学方法制备ZnO纳米颗粒掺杂类金刚石薄膜及其场发射性能研究

采用液相电化学沉积技术制备了ZnO纳米颗粒掺杂的类金刚石(DLC)薄膜, 研究了ZnO纳米颗粒掺杂对DLC薄膜场发射性能的影响. 利用X射线光电子能谱、透射电子显微镜、Raman光谱以及原子力显微镜分别对薄膜的化学组成、 微观结构和表面形貌进行了表征. 结果表明: 薄膜中的ZnO纳米颗粒具有纤锌矿结构, 其含量随着电解液中Zn源的增加而增加. ZnO纳米颗粒掺杂增强了DLC薄膜的石墨化和表面粗糙度. 场发射测试表明, ZnO纳米颗粒掺杂能提高DLC薄膜的场发射性能, 其中Zn与Zn+C的原子比为10.3%的样品在外加电场强度为20.7 V/μm时电流密度达到了1 mA/cm². 薄膜场发射性能的提高归因于ZnO掺杂引起的表面粗糙度和DLC薄膜石墨化程度的增加.     

射频功率对类金刚石薄膜性能的影响

在不同射频功率条件下,实验研究了射频等离子体化学气相沉积类金刚石薄膜的金刚石相分数、光学常数和硬度。利用Raman光谱仪、椭圆偏振仪、数字式显微硬度计分别测试了不同条件下单层类金刚石薄膜的金刚石相分数、光学常数和硬度。实验表明,随着功率的增加,金刚石相的相对分数减少,薄膜的折射率先减小再增加然后减小,射频功率大于910 W时,沉积速率急剧增大。而薄膜的硬度先增加后减小,在射频功率为860 W处获得最大值。     

射频功率对类金刚石薄膜性能的影响

在不同射频功率条件下,实验研究了射频等离子体化学气相沉积类金刚石薄膜的金刚石相分数、光学常数和硬度。利用Raman光谱仪、椭圆偏振仪、数字式显微硬度计分别测试了不同条件下单层类金刚石薄膜的金刚石相分数、光学常数和硬度。实验表明,随着功率的增加,金刚石相的相对分数减少,薄膜的折射率先减小再增加然后减小,射频功率大于910 W时,沉积速率急剧增大。而薄膜的硬度先增加后减小,在射频功率为860 W处获得最大值。     

Determination of the optical bandgap for diamond-like carbon films obtained by laser plasma deposition

We have obtained and analyzed the optical transmission spectra of diamond-like carbon films deposited on quartz substrates by pulsed laser deposition (λ = 1064 nm, τ = 20 nsec, q = 4.9·10⁸ W/cm²) under vacuum (p = 2.6·10⁻³ Pa). Based on the spectra obtained, we have estimated the size of the bandgap by the Tauc method, and also have studied the growth dynamics of the coatings formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 637–641, September–October, 2007.     

Gas barrier properties of diamond-like carbon films coated on PTFE

Diamond-like carbon (DLC) films were deposited on polytetrafluoroethylene (PTFE) using radio frequency (RF) plasma-enhanced chemical vapour deposition (PE-CVD). Before the DLC coating, the PTFE substrate was modified with a N₂ plasma pre-treatment to enhance the adhesive strength of the DLC to the substrate. The influences of the N₂ plasma pre-treatment and process pressure on the gas permeation properties of these DLC-coated PTFE samples were investigated. In the Raman spectra, the G peak position shifted to a lower wave number with increasing process pressure. With scanning electron microscopy (SEM), a network of microcracks was observed on the surface of the DLC film without N₂ plasma pre-treatment. The density of these cracks decreased with increasing process pressure. In the film subjected to a N₂ plasma pre-treatment, no cracks were observed at any process pressure. In the gas barrier test, the gas permeation decreased drastically with increasing film thickness and saturated at a thickness of 0.2 μm. The DLC-coated PTFE with the N₂ plasma pre-treatment exhibited a greater reduction in gas permeation than did the samples without pre-treatment. For both sample types, gas permeation decreased with increasing process pressure.     

Parametric dependence of the properties of pulsed-laser-deposited diamond-like carbon films

The properties of Pulsed-Laser-Deposited Diamond-Like Carbon (PLD DLC) films are studied as functions of the power density and the wavelength of the laser beam, and the incident angle of the beam relative to the normal of the target surface. All the films have a similar structure consisting of graphite particulates embedded in a continuous matrix, so the macroscopic performance of the films is determined by the overall contributions of the particulates and the matrix. The use of higher, shorter, or larger leads to an enhancement of the diamond-like characteristics and a simultaneous increase of the particulate density. These two effects give opposite contributions to the electrical conductivity _R, leading to the following results. (i) _R drops with increasing in the low range (region I) due to the stronger diamond-like nature of the matrix, but increases sharply after has exceeded a threshold _min as a result of the rapid increase in particulate density. (ii) In region I, the use of shorter or larger leads to a more diamond-like matrix, and this overwhelms the degradation effect caused by the slight increase in particulate density. The samples thus become more insulating. In the high region (region II), however, the use of shorter or larger gives rise to higher particulate density, thereby increasing the electrical conductivity.     

衬底温度对类金刚石薄膜力学性能的影响

 采用脉冲激光沉积方法在不同衬底温度下制备了最高硬度与弹性模量分别达45 GPa和290 GPa,且表面十分光滑的类金刚石薄膜。在相对湿度为80%的条件下,薄膜最低的摩擦系数与磨损率分别为0.045与5.74×10^-10 mm³·N^-1·m^-1。实验结果表明,硬度与弹性模量随衬底温度升高而降低,摩擦系数与磨损率随衬底温度升高而增大。拉曼光谱表明:在室温下制备的薄膜为典型类金刚石结构,sp³含量高达76.8%,而随温度升高,薄膜结构逐渐经无定形碳结构向纳米晶石墨结构方向发展,sp³含量也随之降低,力学性能变差。     

离子束辅助沉积对类金刚石膜结构影响的计算机模拟

采用分子动力学(MD)模拟研究了离子束辅助沉积(1BAD)生长类金刚石(DLC)膜的物理过程.分 别选C₂分子和Ar离子作为沉积源和辅助沉积粒子.改变Ar的入射能量和到达比(A r／C)，研 究了它对DLC膜结构的影响.重点讨论了Ar辅助沉积引起表面原子的瞬间活性变化对薄膜结构 产生的影响.分析表明，由于Ar离子的轰击引起的能量和动量的传递，大大地增强了C原子在 表面的反冲动能及迁移概率，增加了合成薄膜的SP³键含量.研究结果和实验 观察一致，并从合成机理上给出了一些定量解释. 关键词： 类金刚石膜 离子束辅助沉积 分子动力学模拟     

Influence of ion bombardment on residual stresses in diamond-like carbon films

The dependence of internal residual stresses in thin diamond-like carbon films grown by the PECVD technique on the most important growth parameters such as the power of the exciting RF discharge and the substrate bias potential is considered. The results have shown that the mechanical stresses in films reach the uppermost value of 1.9 GPa at the smallest values of power and potential. The stress decreases with the growth of both parameters and has only a slight dependence on the film thickness in the range 0.1–1 μm. The bombardment of the obtained films by argon ions with energy of 300 keV and phosphorus ions with energy of 200 keV has resulted in the reduction of compressive stress with the ion dose growth down to its inversion. AFM study of the bombarded films has revealed significant changes in their surface morphology.     

利用强流脉冲离子束技术在室温下沉积类金刚石薄膜研究

利用强流脉冲离子束技术在Si基体上快速大面积沉积类金刚石(DLC)薄膜.电压为250kV,束流密度为250A·cm-2,脉宽为80—100ns,能流密度为5J·cm-2的离子束(主要由碳离子和氢离子组成)聚焦到石墨靶材上,使石墨靶材充分蒸发和电离,在石墨靶的法线方向的Si基体上沉积非晶的碳薄膜.Raman谱分析显示,所沉积薄膜为类金刚石薄膜.随着靶材与基体之间距离的减小,薄膜中sp3碳成分含量增加,同时硬度值也有所增大,并且薄膜的摩擦系数和表面粗糙度增加.x射线光电子能谱(XPS)分析显示薄膜中的sp3碳 关键词： 强流脉冲离子束 类金刚石薄膜 XPSRaman谱分析     

Fabrication of ZnO nanoparticles-embedded hydrogenated diamond-like carbon films by electrochemical deposition technique

ZnO nanoparticles-embedded hydrogenated diamond-like carbon (ZnO-DLC) films have been prepared by electrochemical deposition in ambient conditions. The morphology, composition, and microstructure of the films have been investigated. The results show that the resultant films are hydrogenated diamond-like carbon films embedded with ZnO nanoparticles in wurtzite structure, and the content and size of the ZnO nanoparticles increase with increasing deposition voltage, which are confirmed by X-ray photoelectron spectroscopy (XPS), Raman, and transmission electron microscope (TEM). Furthermore, a possible mechanism used to describe the growth process of ZnO-DLC films by electrochemical deposition is also discussed.     

An effective reflectance method for designing broadband antireflection films coupled with solar cells

The solar spectrum covers a broad wavelength range,which requires that antireflection coating(ARC) is effective over a relatively wide wavelength range for more incident light coming into the cell.In this paper,we present two methods to measure the composite reflection of SiO2/ZnS double-layer ARC in the wavelength ranges of 300-870 nm(dualjunction) and 300-1850 nm(triple-junction),under the solar spectrum AM0.In order to give sufficient consideration to the ARC coupled with the window layer and the dispersion effect of the refractive index of each layer,we use multidimensional matrix data for reliable simulation.A comparison between the results obtained from the weighted-average reflectance(WAR) method commonly used and that from the effective-average reflectance(EAR) method introduced here shows that the optimized ARC through minimizing the effective-average reflectance is convenient and available.     

An effective reflectance method for designing broadband antireflection films coupled with solar cells

The solar spectrum covers a broad wavelength range, which requires that antireflection coating (ARC) is effective over a relatively wide wavelength range for more incident light coming into the cell. In this paper, we present two methods to measure the composite reflection of SiO₂/ZnS double-layer ARC in the wavelength ranges of 300-870 nm (dual-junction) and 300-1850 nm (triple-junction), under the solar spectrum AM0. In order to give sufficient consideration to the ARC coupled with the window layer and the dispersion effect of the refractive index of each layer, we use multi-dimensional matrix data for reliable simulation. A comparison between the results obtained from the weighted-average reflectance (WAR) method commonly used and that from the effective-average reflectance (EAR) method introduced here shows that the optimized ARC through minimizing the effective-average reflectance is convenient and available.